Water-soluble disazo compounds containing a pyrazole component

ABSTRACT

Water-soluble disazo dyes of the pyrazole series of the formula   A and B each being hydrogen, methyl or phenyl; X being a phenyl or naphthyl radical; Y being a divalent phenylene or naphthylene radical; R being hydrogen or an organic radical; and n being 1 or 2. The dyes are especially suitable for dyeing and printing natural and synthetic polyamides and basified textile material and also for dyeing cellulose fibers, particularly when they contain reactive radicals.

United States Patent [191 Dehnert [4 1 Aug. 19, 1975 1 WATER-SOLUBLEDISAZO COMPOUNDS CONTAINING A PYRAZOLE COMPONENT [75] Inventor: JohannesDehnert, Ludwigshafen,

Germany 22 Filed: Feb. 20, 1973 21 Appl. No.: 333,783

[30] Foreign Application Priority Data Feb. 26, 1972 Germany 2209255[52] US. Cl. 260/160; 260/153; 260/154; 1

260/158; 260/176; 260/194; 260/197; 260/200; 260/205; 260/206 [51] Int.Cl C09b 43/00; D06p 1/06; D06p 1/38 [58] Field of Search 260/160, 161,159, 153, 260/154 [56] References Cited UNlTED STATES PATENTS 1,706,8783/1929 Geller 260/160 1,828,599 10/1931 de Montmollin et a1. 260/1603,037,974 6/1962 Kracker et al. 260/160 3,158,597 11/1964 Blass et a1260/160 X 3,234,206 2/1966 Liechti 260/160 X 3,449,317 6/1969 deMontmollin 260/161 3,462,409 8/1969 Meininger 260/160 X 3,549,61212/1970 Clarke 260/160 3,663,528 5/1972 Ramanathan... 260/160 3,663.5305/1972 Leroy et a1. 260/160 3,755,290 8/1973 de Montmollin et al.260/161 OTHER PUBLlCATlONS Behr et al., Pyrazoles, Pyrazolines,Pyrazolidines, 1n-

dazoles and Condensed Rings, Interscience Publishers, New York, 1967,Pages 10-16.

Fierz-David et al., Fundamental Processes of Dye Chemistry,Intersciences Publishers, New York, 1949, Pages 82-85.

Primary ExaminerFloyd D. l-Iigel Assistant Examiner-C. F. WarrenAttorney, Agent, or Firm.lohnst0n, Keil, Thompson & Shurtleff [5 7ABSTRACT Water-soluble disazo dyes of the pyrazole series of the formulaC (so H) E1; 3 n

A and B each being hydrogen, methyl or phenyl; X being a phenyl ornaphthyl radical; Y being a divalent phenylene or naphthylene radical; Rbeing hydrogen or an organic radical; and n being 1 or 2. The dyes areespecially suitable for dyeing and printing natural and syntheticpolyamides and basified textile material and also for dyeing cellulosefibers, particularly when they contain reactive radicals.

3 Clain'ns, No Drawings in which A is hydrogen, methyl or phenyl;

B is hydrogen, methyl or phenyl;

X is a benzene or naphthalene ring which may bear chloro, bromo, methyl,methoxy, ethoxy, nitro and/or sulfamyl as single to triple substituents;

Y is a benzene or naphthalene ring attached in the 1,4- position to theazo bridges and which may bear chloro, bromo, methyl, methoxy, ethoxy,nitro and/or sulfamyl as single to triple substituents;

R is hydrogen or an unsubstituted or substituted aliphatic,cycloaliphatic, aromatic or araliphatic radical; Z is a fiber-activeradical;

m is zero or 1; and

nis1,2,3or4.

X and Y may bear from one to three of the substituents chloro, bromo,methyl, methoxy, ethoxy, nitro and/or sulfamyl and each may also bearone or more sulfo groups and a fiber-active radical Z, the total numberof substituents for each of X and Y not as a rule being more than 3.

Methyl groups are particularly preferred for A and B.

The substituent R on the pyrazole ring is hydrogen or an unsubstitutedor substituted aliphatic, cycloaliphatic, aromatic or araliphaticradical. Examples of substituents for R are: hydroxy, cyano, amino,chloro, sulfo and nitro. R may also bear a fiber-active radical Z as asubstituent. Examples of radicals R are: alkyl of one to seven carbonatoms, hydroxyalkyl of two or three carbon atoms, aminoalkyl of two orthree carbon atoms, cyanoalkyl of two or three carbon atoms or phenyl orphenyl bearing chloro, nitro, cyano, amino or alkyl as a substituent.Specific examples are methyl, ethyl, propyl, butyl, cyclohexyl,hydroxyethyl, aminoethyl, cyanoethyl, phenyl and benzyl.

Examples of fiber-active radicals Z which the entire molecule of theformula (I) may bear once are: -COCH=CH COCBr=CH -CO-CH -Cl, -COCH CHCl,

S l -c1 C1 --CO I N -CO b} N-" c1 CO-CH=CH 2 CH -N CON CH -N CO-CH=CHThe number of sulfonic acid groups (n) in the whole molecule of formula(I) is l, 2, 3 or 4. They may be located on the rings X or Y or in thesubstituents A, B, R or Z.

The new dyes of formula (I) may be prepared for example by coupling adiazo compound of an amine of the formula: X-N=NYNH with a couplingcomponent of the formula:

and reacting the product of the formula:

C-OH

with a hydrazine of the formula:

H NNH-R and if desired introducing the radical Z. X, Y, A, B, R and Zhave the meanings given above. All the reactions may be carried out byconventional methods. The sulfonic acid group may be already present asa substituent in the reactants. In cases in which the dye molecule iseasily sulfonatable in the aromatic nuclei the sulfo group may beintroduced into the finished disazo dye, the starting compound thenbeing:

It is also possible to introduce the SO H- group into the molecule byesterifying with sulfuric acid an aliphatic hydroxyl group alreadypresent in the molecule.

The fiber-active radicals in the new dyes are reactive groups whichenable the dye to combine chemically with the substrate, preferablycellulose. These radicals may be introduced into the molecule by aconventional method for example by reacting the dye by way of an aminoor sulfamoyl group or another function capable of reacting with areactive polyfunctional compound such as hexahydro-l,3,5-triacryloxy-S-triazine or cyanuryl chloride or a derivativethereof.

When the synthesis of the dyes is carried out in one of the waysdescribed above with a 1,3-dicarbonyl compound as the couplingcomponent, one of the following compounds is conveniently used as the1,3-dicarbonyl compound: malonodialdehyde, acetoacetaldehyde,acetylacetone, formylacetophenone, benzoylacetone, dibenzoylmethane or aderivative of these compounds such as dimethylaminoacrolein or4-diethylaminobutenone-2 in which case after coupling is complete thecoupling product is present in the form of the 1,3- dicarbonylazo dye.

The new disazopyrazole dyes are particularly suitable for dyeing andprinting natural and synthetic polyamides, wool, leather and all typesof basified textile material by conventional methods.

Dyes with reactive groups are especially suitable for dyeing cellulosicmaterial. The reactive groups may however also be introduced duringdyeing. Triacryloformal for example is suitable for this purpose. Dyesaccording to the invention and provided with reactive groups give fulldyeings having excellent fastness properties on textile materialspreferably containing cellulose.

The following Examples illustrate the substances of the invention, theirproduction and their use in detail. The parts and percentages set outare by weight. Parts by volume bear the same relation to parts by weightas the liter to the kilogram.

A solution of 357 parts of the disodium salt of 4-aminoazobenZene-3,4'-disulfonic acid in 1500 parts of water at 40C has300 parts by volume of 23% sodium nitrite solution added to it and isallowed to flow over one hour into a mixture of 250 parts by volume oflON hydrochloric acid and 1000 parts of ice, the whole is stirred for 2hours at 0 to 5C and the excess nitrous acid is destroyed with a littlesulfamic acid.

The diazotization mixture thus prepared has added to it at 0 to 5C 1 10parts of acetylacetone and then in portions 150 parts of anhydroussodium acetate until a pH of 4.0 to 4.5 has been reached, a clear dyesolution thus being obtained.

After coupling is over the dye solution is adjusted to pH 7 to 9 byadding parts by volume of 50% caustic soda solution and then 89 parts ofdihydrazine sulfate is added. 40 parts by volume of 50% caustic sodasolution is added in the course of one hour After stirring for severalhours at room temperature the condensation is over and the dye partlyprecipitated. To complete precipitation 1000 parts of sodium chloride isadded and the whole is stirred for another hour and suction filtered.After drying at 80C in vacuo an orange yellow powder is obtained whichdissolves in water with a yellow color.

Light fast yellow dyeings having good wet fastness properties areobtained on wollen cloth from a sulfuric acid liquor and onpolycaprolactam from an acetic acid liquor.

Dyes having similar fastness properties are obtained in an analogous wayusing equivalent amounts of the aminoazobenzenes or aminoazonaphthalenesgiven in the following Table. They are also suitable for dyeing cottonby the process of Example 12.

Example Diazo component SO H y HOESQN N m Shade of dyeing onpolycaprolactam or cotton yellow orange reddish orange orange orangereddish orange yellowish red orange yellowish red orange EXAMPLE 12 20parts of the dye powder of Example 1, 30 parts of sodium hydrogencarbonate, 15 parts of hexahydrol,3,5-triacryloyl-S-triazine, 3 parts ofpolyvinyl alcohol and 12 parts of the condensation product fromformaldehyde and naphthalene-Z-sulfonic acid are mixed with 100 parts ofurea, 420 parts of water and 400 parts of sodium alginate thickening(which contains 40 parts of alginate dry substance in 1000 parts ofwater). Cotton cloth is printed with the resultant print paste, driedand then steamed for about 5 to 8 minutes at 100C. The printed materialis then rinsed and soaped as usual. Yellow prints having very good lightand wet fastness properties are obtained EXAMPLE 1 3 CH @N N N NGQ E 30parts by volume of 23% sodium nitrite solution is gradually added to amixture of 20 parts of finely divided 4-aminoazobenzene in 40 parts ofconcentrated hydrochloric acid, 400 parts of water and 200 parts of iceand the whole is stirred for two hours at +10C. Ex-

cess nitrous acid in the filtered diazo solution is removed in the usualway. 11 parts of acetylacetone is then added all at once and then 55%sodium acetate solution is added at 10 to 15C until a pH of 4 to 5 isreached. The yellow coupling product which is sparingly soluble in wateris suction filtered and washed with water. This paste has 600 parts ofpyridine, 150 parts of water and 40 parts of phenylhydrazine-4- sulfonicacid added to it and is then stirred at 70 to 80C until completereaction has been achieved, this being detected chromatographically. Thereaction mixture is introduced into 600 parts of water and the dye isprecipitated by adding 200 parts of sodium chloride. The dye is isolatedand dried. It is a yellowish brown powder which dissolves in water witha yellow color and gives yellow dyeings having excellent fastnessproperties on polycaprolactam and on wool.

EXAMPLE 14 OCH 5 5 A or N 3 ocH CH3 EXAMPLE l5 A mixture of 30 parts byvolume of a 23% solution of sodium nitrite and a solution of 32 parts ofthe sodium salt of 4-aminoazobenzene-4-sulfonic acid in 500 parts ofwater is allowed to flow gradually at 10 to 15C into a mixture of 40parts of ION hydrochloric acid, 100 parts of ice and 200 parts of water.After stirring for two hours at 10 to 15C the excess is destroyed withsulfamic acid as usual.

1 1 parts of acetylacetone is gradually introduced into thediazotization mixture and then 50% sodium acetate solution is addeduntil a pH of from 4.5 to 5 is reached. After the coupling is over thecoupling product is suction filtered and washed with a little water. Themoist paste of the coupling product is stirred with 1500 parts of waterand after 10 parts of hydrazine hydrate has been added the whole isstirred at room temperature until starting product is no longerdetectable. The dye is precipitated from the deep yellowish red solutionby adding parts of sodium chloride, suction filtered and washed with alittle water and dried at 80C. An orange red powder is obtained whichdissolves in hot water with a yellowish red color. Golden yellow dyeingshaving outstanding light fastness and good wet fastness properties areobtained with the dye on fibers or cloth of polyamide or wool.

By following the above procedure but using the equivalent amounts of theaminoazobenzenes or aminoazonaphthalenes specified in the followingTable as diazo components, dyes of similar tinctorial properties and thespecified shades are obtained.

Example Diazo component Shade of dyeing on polycaprolaczam 16 -N=N- -NHyellow H0 5 17 N=N4 Q E-NH reddish yellow H0 8 CH CPI 18 N=N-\ -NHreddish yellow E10 8 CH Example Diazo component Shade of dyein 0T1polycaprclaccam OCH OCH

OCH

0cm 3 CA OQMNQYH a OCH:

QN N Q4": x0

yellowish orange yellowish red yellowish red yellowish red reddishorange orange yellow reddish orange reddish orahge orange yellowreddishorange orange 11 g 12 EXAMPLE 52 The coupling product of Example 15,paragraph 2, is OCH CH stirred at 60C with 500 parts by volume ofpyridine. N-C H Into the solution thus obtained there is introduced@-N=N N=N gradually a mixture of 17 parts of phenyl hydrazine and 1 N 550 parts by volume of pyridine and the reaction mix- B CH5 CH3 ture iskept at 60C while stirring until complete reac- 0 1 mole of the p gProduct of tion has taken place. This may easily be determined bymt'hyLS methoxyazobenzene 3, sulfonic acid and th n layerchromatography. After cooling the reaction acetylacetone obtainedanalogously to Example 15 is F (muted 5000 parts of wate'r and the fstirred as a moist paste with 1000 parts of water and adprFclpnated byafidmg 300 parts i Sodium Chlondejusted to pH with caustic sodasolution. Then parts T lsolat ed and dned dye (a yellowlsh brown powder)of cyanoethylhydrazine is added and the whole is dissolves in hot waterwith a reddish yellow color and heated to C. After reaction is completedthe dye is wool or polyamlde fibers re ddish yellow Shades precipitatedby adding saturated sodium chloride solul S havmg very good fastnesspropemes' tion, suction filtered, washed with a little water and EXAMPLE40 dried. The ocher colored powder dissolves in hot water 3 giving areddish yellow color. Yellowish orange dyeings with excellent fastnessproperties are obtained there- 0 N=N N with on polycaprolactom or woolencloth. 20 The following dyes are obtained in a similar manner: 5

Example Dye Shade of dy ing on polycapr'olaotam CH NCH CH CN .53 HO SNN@-N Nil yellow N'C" ClI cN yellow 110 61 CH3 t A 1 N-CH2CH2CN N N ..N Nreddish yellow 1 N cn CH3 OCH CH 5 56 @N N N N 2 Z reddish orange CH H08 OCH 5 N-CH -CH CN 57 N N N l o a HO S 3 CH 38 -N N N N- i 2 2 orange OH S 5 CH CN 39 N N N =.N 2 2 orange l so H 5 EXAMPLE 41 Cl-l l I-CH -CH-OS H 3N CH 1 1 parts of acetylacetone is added at 5 to C to thesolution of the diazonium salt from parts of 4- aminoazobenzene obtainedin the usual way and then saturated sodium acetate solution is addedgradually until a pH of 5 has been reached. The coupling product issuction filtered and washed with water. The powder obtained after dryingis boiled with 5000 parts by volume of ethanol while stirring. A mixtureof 10 parts of 2-hydroxyethylhydrazine and 20 parts by volume of ethanolis slowly added and the whole is kept for about 2 hours under refluxingconditions until starting dye can no longer be detectedchromatographically.

After cooling the reaction product of the formula:

is suction filtered, washed with alcohol and dried.

The whole of the pyrazole derivative thus obtained is introduced insmall portions into 200 parts of 100% sulfuric acid while stirring sothat the temperature of 40C is not exceeded. Toward the end the whole isstirred for some time at 50C until starting product is no longer to bedetected. The reaction mixture is then introduced into 1500 parts of amixture of ice and water and the dye is isolated by suction filtrationand washing with water. For conversion into the sodium salt the moistpaste is suspended in 2000 parts of water and 400 parts by volume of 55%sodium acetate solution is introduced. After stirring for several hoursthe sodium salt of the dye sulfuric acid ester is suction filtered,washed with a little water and dried at 80C. The orange yellow powderdissolves in hot water with a yellow color and gives yellow dyeingshaving excellent fastness properties on polycaprolactam or woolen cloth.

' EXAMPLE 42 One tenth of the coupling solution obtained according toExample 1, paragraph 2 is adjusted to pH 7.5 with 50% caustic sodasolution and at room temperature 12 parts of Z-aminoethylhydrazine isadded. The whole is stirred for several hours until starting product isno longer detectable and the dye is then precipitated by adding 100parts by volume of lON hydrochloric acid and 100 parts of potassiumchloride, suction filtered and washed with a little water and dried. Thewater-soluble yellow powder obtained dyes polyamide fast reddish yellowshades.

The solution of 26 parts of the dye obtained according to Example 42 in200 parts of water which has been adjusted to pH 7 has gradually addedto it at 0 to 5C while stirring a solution of 10 parts of cyanurylchloride in 150 parts by volume of acetone. A pH range of from 5 to 7 ismaintained at the same time by adding sodium hydrogen carbonate. Thereaction product is precipitated by adding parts of potassium chloride,suction filtered, washed with dilute potassium chloride solution anddried in vacuo at 40C. The yellow powder obtained, when dissolved inwater, gives yellow shades of excellent fastness properties on cotton bythe various methods conventionally used for reactive dyes.

A solution of 26 parts of the dye of Example 42 prepared as described inExample 43 is stirred with a solution of 15 parts of the sodium salt of1,3-dichloro-5- aminobenzenesulfonic acid triazine:

cl-g

NH so Na 34 parts of 4-amino-2,5-dimethoxyazobenzene-3- sulfonic acid isdiazotized as described in Example 15, paragraphs 1 and 2 and coupledwith l 1 parts of acetylacetone. The dye paste obtained after isolationis dissolved in water at 50C with an addition of caustic soda solutionto bring the pH to 7.5. Then 12 parts of 2-aminoethylhydrazine is addedand the whole is stirred at 50C until reaction is completed. Thereaction product is substantially precipitated by adding 500 parts ofsodium chloride and it is then suction filtered and washed with a littlewater. The brownish powder obtainable after conversion analogous toExample 44 dissolves in water with a yellowish red color. Fast reddishorange shades are obtained on cotton by the more important conventionalreactive dyeing methods.

EXAMPLE 46 The diazotization mixture obtained as described in Example 15from 32 parts of the sodium salt of 4-aminoazobenzene-4-sulfonic acidhas 14 parts of 3-diethylaminopropenal-( 1) added to it at from 5 to C.Coupling is over after stirring for several hours. The coupling productis suction filtered and washed with water. The paste thus obtained isstirred with 2000 parts of water and adjusted to a pH of 7 with dilutecaustic soda solution. After 10 parts of hydrazine hydrate has beenadded the whole is stirred at room temperature until complete reactionhas been achieved. The new dye is precipitated from the solution thusobtained by adding 500 parts of sodium chloride. After suctionfiltration, washing with a little water and drying there is obtained ayellowish brown powder whose yellow aqueous solutions give fast reddishyellow shades on hexamethylenediamine adipate fibers.

EXAMPLE 47 CH )rN 18 parts of 4-diethylaminobutenone-(2) is used insteadof 3-diethylaminopropenal-(1) in Example 46 and the procedure of thatExample is otherwise re peated. A yellowish brown dye powder is obtainedwhich dissolves in water and gives fast reddish yellow dyeings on wooland synthetic polyamide.

EXAMPLE 48 CPL The diazotization mixture of Example is allowed to flowgradually at 0 to 5C into a solution of 18 parts of benzoylacetone in1000 parts by volume of dimethylformamide. The reaction mixture then hasslowly added to it 250 parts by volume of a 50% sodium acetate solutionand, after coupling is over, 400 parts of sodium chloride.

The suction filtered and washed coupling product is stirred with 1500parts of water and 10 parts of hydrazine hydrate at 50C until thereaction is over. After dilution with 2000 parts of water and saltingout with 100 g of sodium chloride the new dye is isolated by suctionfiltration and washed and dried. The orange yellow powder dissolves inhot water with a yellow color. The yellow dyeings obtained therewith onwoolen or polycaprolactam textile materials have high light fastness andgood wet fastness properties.

EXAMPLE 49 The procedure described in the preceding Example is repeatedusing 17 parts of formylacetophenone in stead of benzoylacetone ascoupling component. A reddish yellow dye is obtained having similartinctorial propertiesv EXAMPLE 50 One tenth of the diazotization mixtureprepared as described in Example l is allowed to flow gradually at 0 to5C into a solution of 25 parts of dibenzoylmethane in 1000 parts byvolume of dimethylformamide. At the same time 100 parts by volume of 50%sodium acetate solution is added to the coupling mixture. After thecoupling is over the dye is diluted with 2000 parts of water andprecipitated by adding 500 parts by volume of saturated sodium chloridesolution, washed with a little water and dried. The orange powderdissolves in water with a yellow color and gives light fast yelloworange dyeings having good wet fastness properties on polyamide orwoolen cloth.

EXAMPLE 51 and The coupling product with benzoylacetone obtainableaccording to Example 48, paragraph 1 is stirred as the isolated moistpaste with 500 parts by volume of pyridine at 60C. Then a mixture of 15parts of phenyl hydrazine and 50 parts of pyridine is gradually addedand the whole is kept at 60C until starting dye is no longer detectable.6000 parts of water and 300 parts of glacial acetic acid are added,followed by 1000 parts of sodium chloride to isolate the dye. Theisolated and dried dye (a brown yellow powder) dissolves in hot waterwith a reddish yellow color. Polyamide or woolen threads are dyedtherewith fast reddish yellow shades.

EXAMPLE 52 16 parts of the dye of Example 1 is intensely ground as a drypowder with 10 parts of hexahydro-1,3,5-

triacryloyl s triazine in a vibrating mill in dry condition. An easilywater-soluble yellow product is thus formed which is applied to cottonfor example by the pad-stcam method. Yellow dyeings having outstandinglight and wet fastness properties are obtained. Fast yel low shades withexcellent fastness properties are also obtained therewith on polyamide.

are obtained.

with caustic soda solution, 12 parts of 2-hydroxyethylhydrazine is addedand the whole is stirred at 40C until complete reaction has beenachieved. The dye is precipitated by adding saturated sodium chloridesolution and heating to 90C. After suction filtration, washing with alittle water and drying, the dye is a brown yellow Example No. Startingdye Shade of dyeing on cotton I 53 N=N N=N i yellow =N H 8 CH 3 NH Q Q Iyellow H035 cu cs 0C5, cs

H 55 u--- j 4=- l reddish orange w ocn on so u OCH cu 3 3 4! N=N N=H. 56a0 5 t orange 3 J PM ocu CH3 SO H CH 3 2 t 57 HO 5 N=ll ;-.l=I-l-(reddish yellow CH 58 HO S4 N=N HEN-ii orange ca, 0 H J c? OCH 3 50 a F 3NH 59 N=N N=H L yellowish red OCH3 Cll so s 0E2 N=N N=N orange 60 H0 8so n 303K 7 CH3 6 N=N \yN=N-) orange EXAMPLE 62 60 powder whose aqueoussolutions give yellow dyeings The coupling product prepared as describedin Ex ample 15, paragraph 2 is suspended as a moist paste in 500 partsof water. The mixture is adjusted to pH 7.5

having high light fastness and good wet fastness propcrties onpolycaprolactam or woolen cloth.

The following dyes, prepared analogously, have similar tinctorialproperties: 65

Ex- Shade of dyeing ample Dye on poiycapro N0. lactam CH 6) f -Uli, -Cli-oi:' Yellow N=N N=l\lv v v d 0 (J 9 CH. CH 64 r yellow -NCH, (,H. 0HN=N- Nat-4 I A d 110 s CH (JH j -CH, CH, OH 0: Ho N=N N=N*% I 2 yellow/:.N 11H CH 3 CH C l 3 b6 5 2 2 yeilowlsh orange N=N N=N l HO 5 F j boHCH' O CH- CH -CH OH 67 (ll-i N=N reddish orange x CH SOt H Obi-l. b CH.N CH..-CH/ OH --N=N- N=N-% l d 2 Orange 1 "N CH SO H 4 9H5 ll H OH F 22" orange 9 L N V on. so a 3 ,0 (1H CH \l 01;, OH -0:l 4, W I: j g 2letitllcli Oran, IL s-g ami N N EXAMPLE 71 at C.

CH 5g 18 parts of the yellow powder thus obtained is intro- 3 i ducedinto parts of sulfuric acid monohydrate while stirring at a maximum of40C. 86 parts of 65% oleum is added to the solution thus obtained andthe whole is stirred at 25 to 30C until complete sulfonaso H 60 tion hastaken place. The whole is discharged into I000 3 parts of a mixtureofice and water and the free d e acid y A diazonium salt solutionobtained from 4- is isolated by suction filtration and washing withwater. aminobenzenc by a known method is allowed to flow The product isstirred with 1000 parts of water and at from 5 to 10C into a solution of17 parts of benzoyneutralized by adding a 10% solution of sodiumcarlacetone in 1000 parts of dimethylformamide. At the n C SO that theSodium Salt of the dye which is sparsame time a saturated solution ofsodium acetate is added until a pH of 4.5 is reached. The coupling product thus obtained is suction filtered, washed with 1000 parts of 50%alcohol and then with hot water and dried ingly soluble in cold water isformed. The dye is isolated and dried. lt is a yellow powder whichdissolves in hot water. The solution dyes polyhexamcthylcnediamineadipate cloth fast yellow shades.

2 1 MEkE ,2

, C Q H A solution of 4 parts of phenyl hydrazine-4-sulfonic acid inparts of pyridine and parts of water is 15 gradually run at 60C into amixture of 50 parts of pyridine and 4 parts of the dried couplingproduct obtainable according to Example 71, paragraph 1. The reactionmixture is stirred at 60C until complete reaction has been achieved.After cooling it is introduced into 1000 parts of water while stirring.The new dye is precipitated from the resulting solution by adding 40parts of sodium chloride, suction filtered, washed with alcohol anddried. An orange powder is obtained whose aqueous solutions dyepolycaprolactam cloth fast yellow shades.

EXAMPLE 73 and A solution of 8 parts of phenylhydrazine4-sulfonic acidin 20 parts of pyridine and parts of water is added gradually at C to amixture of one fifth of the paste of the coupling product prepared asdescribed in Example 48, paragraph 1 and 100 parts of 75% pyridine. Thewhole is kept at 60C while stirring until starting dye can no longer bedetected. After introduction into 1000 parts of water and salting outwith 150 parts of sodium chloride, the reaction product is isolated bysuction filtration, washing with alcohol and drying at C. The reddishyellow powder dissolves readily in water with a reddish yellow color andproduces golden yellow dyeings having excellent fastness properties onpolyar'nide fibers.

By following Example 43 but using the reactive components given belowinstead of the cyanuryl chloride component, yellow water-solublereactive dyes are obtained which are outstandingly suitable for dyeingcellulosic textile material.

Dye

Reactive component The following dyes can be obtained analogously toExample 42:

ougll By introducing reactive radicals into dyes of the and wettreatments preferably on cellulosic textile maabove Examples 91 to 95products are obtain'fible 25 terial by conventional dyeing and printingmethods: which give orange dyeings having high fastness to light ampleDye II I! CH 0P 0 Cl -CO--CH=CH CH. SO H 0.1 mole of the couplingproduct of the formula:

HO-CH -CH "S02 Q N:

I 03m. B

in which A is hydrogen, methyl or phenyl;

B is hydrogen, methyl or phenyl;

X is phenyl; naphthyl; or phenyl substituted by chloro, bromo, methyl,methoxy, ethoxy, nitro or sulfamoyl;

Y is p-phenylene; p-phenylene substituted by chloro,

bromo, methyl, methoxy or ethoxy; or 1,4- naphthylene;

R is hydrogen; alkyl of l to 7 carbon atoms; hydroxyalkyl of 2 or 3carbon atoms; aminoalkyl of 2 or 3 carbon atoms; cyanoethyl; cyclohexyl;benzyl; phenyl; or phenyl substituted by chloro, nitro, cyano, amino ormethyl; and

n is 1 or 2, the sulfo groups being bound to X, Y or 2. A dye as claimedin claim 1 wherein R is hydrogen, ethyl, hydroxyethyl, aminoethyl,cyanoethyl, phenyl, chlorophenyl, nitrophenyl, cyanophenyl, aminophenylor methylphenyl.

3. A dye as claimed in claim 1 wherein A and B each represents methyl.

1. A WATER-SOLUBLE DISAZO DYE OF THE FORMULA
 2. A dye as claimed inclaim 1 wherein R is hydrogen, ethyl, hydroxyethyl, aminoethyl,cyanoethyl, phenyl, chlorophenyl, nitrophenyl, cyanophenyl, aminophenylor methylphenyl.
 3. A dye as claimed in claim 1 wherein A and B eachrepresents methyl.